Heterogeneous Catalysts for Petrochemical Synthesis and Oil Refining, 2nd Edition

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Industrial Catalysis".

Deadline for manuscript submissions: closed (30 September 2023) | Viewed by 9889

Special Issue Editors


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Guest Editor
Faculty of Chemistry, Department of Petroleum Chemistry and Organic Catalysis, Lomonosov Moscow State University, GSP-1, 1-3 Leninskiye Gory, 119991 Moscow, Russia
Interests: petroleum chemistry; heterogeneous catalysis; oil refining; metal–organic frameworks; dendrimers; zeolites; structured mesoporous aluminosilicates; hydroformylation
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Guest Editor
1. Faculty of Chemical and Environmental Engineering, Department of Physical and Colloid Chemistry, Gubkin Russian State University of Oil and Gas, 65 Leninsky Prospekt, 119991 Moscow, Russia
2. Faculty of Chemistry, Department of General Chemistry, Lomonosov Moscow State University, GSP-1, 1-3 Leninskiye Gory, 119991 Moscow, Russia
Interests: aluminosilicate nanotubes; zeolites; nanostructured mesoporous materials; aluminosilicate nanomaterials; catalytic cracking; hydroprocessing; isomerization
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Heterogeneous catalysis is among the major solutions for cost-effective and sustainable industrial application and processing. The design and development of highly efficient and stable heterogeneous catalysts represent an emergent frontier for overcoming energy and environmental challenges. Many industrial petrochemical and oil refining processes are faced with new challenges that can be solved using heterogeneous catalysts. In particular, the design of new types and improvements of  zeolites, ordered mesoporous and hierarchical systems as well as tuning parameters of active phase deposition are crucial for optimizing of exiting and novel catalysts production.

This Special Issue aims to cover the most recent progress and advances in the field of heterogeneous catalysts based on aluminosilicates, including zeolites and mesoporous materials, MOFs, COFs, and PAFs for petrochemical synthesis and oil refining. This includes, but is not limited to, hydroprocessing (including hydrotreating, isomerization, reforming, etc.), sulfur removal, catalytic cracking, C-1 chemistry, alcohols, fatty acids, and valuable chemicals synthesis.

Prof. Dr. Eduard Karakhanov
Dr. Aleksandr Glotov
Guest Editors

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Keywords

  • petrochemical synthesis
  • oil refining
  • zeolites
  • aluminosilicates
  • organic and metal–organic frameworks
  • nanotubes
  • hydroprocessing
  • C-1 chemistry

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Published Papers (6 papers)

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Research

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12 pages, 1960 KiB  
Article
Thermal Degradation Kinetics of Vacuum Residues in the Presence of Chrysotile Supported Ni-Ti Catalyst
by Nazerke Balpanova and Murzabek Baikenov
Catalysts 2023, 13(10), 1361; https://doi.org/10.3390/catal13101361 - 11 Oct 2023
Cited by 1 | Viewed by 942
Abstract
For the first time, thermal decomposition of vacuum residue and a mixture of vacuum residue with binary nanocatalysts based on leached and non-leached chrysotile with applied active metals was studied using the thermogravimetry method. It is shown that the thermokinetic parameters of decomposition [...] Read more.
For the first time, thermal decomposition of vacuum residue and a mixture of vacuum residue with binary nanocatalysts based on leached and non-leached chrysotile with applied active metals was studied using the thermogravimetry method. It is shown that the thermokinetic parameters of decomposition of vacuum residue and its mixture with binary nanocatalyst are different. The phase composition of the binary nanocatalyst was established through X-ray phase analysis (XRD): (Mg3Si2O5 (OH), NiO and Ti (SO4)2). The quantitative content of elements on the chrysotile surface was determined using X-ray fluorescence analysis: (Ni (4.88%), Ti (7.29%), Si (24.93%), Mg (7.83%), Fe (0.69%) and S (3.89%)). Using atomic emission spectral analysis, the gross quantitative content of supported metals on chrysotile was determined: Ni (4.85%) and Ti (4.86%). A transmission electron microscope showed the presence of finely dispersed particles adsorbed on the surface of and possibly inside chrysotile nanotubes with sizes ranging from 5 to 70 nm. The acidity of the nanocatalyst obtained from the leached active-metal-supported chrysotile was 267 μmol/g and the specific surface area of the nanocatalyst was 54 m2/g. The Ozawa–Flynn–Wall (OFW) method was used to calculate the kinetic parameters of the thermal degradation of vacuum residue and the mixture of vacuum residue with nanocatalysts. Using the isoconversion method, the average values of activation energies and the pre-exponential factor were calculated: 147.55 kJ/mol and 3.37·1016 min−1 for the initial vacuum residue; 118.69 kJ/mol and 1.54·1018 min−1 for the mixture of vacuum residue with nanocatalyst obtained from non-leached chrysotile with applied metals; 82.83 kJ/mol and 2.15·1019 min−1 for the mixture of vacuum residue with nanocatalyst obtained from leached chrysotile with applied metals. The kinetic parameters obtained can be used in modeling and designing the processes of thermal degradation and hydroforming of heavy hydrocarbon raw materials. Full article
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15 pages, 6244 KiB  
Article
Properties of CrOx/MCM-41 and Its Catalytic Activity in the Reaction of Propane Dehydrogenation in the Presence of CO2
by Maria Igonina, Marina Tedeeva, Konstantin Kalmykov, Gennadiy Kapustin, Vera Nissenbaum, Igor Mishin, Petr Pribytkov, Sergey Dunaev, Leonid Kustov and Alexander Kustov
Catalysts 2023, 13(5), 906; https://doi.org/10.3390/catal13050906 - 19 May 2023
Cited by 3 | Viewed by 1429
Abstract
Propylene is an important raw material for the production of many valuable compounds, especially polypropylene, the consumption of which continues to grow every year. The reaction of oxidative dehydrogenation of propane, where carbon dioxide is used as a mild oxidant, is a promising [...] Read more.
Propylene is an important raw material for the production of many valuable compounds, especially polypropylene, the consumption of which continues to grow every year. The reaction of oxidative dehydrogenation of propane, where carbon dioxide is used as a mild oxidant, is a promising method for producing propylene. At the same time, the problem of utilization of greenhouse gas CO2 is partially solved. The synthesis and analysis of the physicochemical properties of mesoporous silicate MCM-41 and supported catalysts CrOx/MCM-41 prepared on its basis were carried out. These catalysts were prepared using incipient wetness impregnation. The support and catalysts were characterized by the methods of low-temperature nitrogen adsorption, TG-DTA, XRD, SEM, TPR-H2, UV/Vis diffuse reflectance spectroscopy, and small-angle X-ray scattering. It is shown that chromium is present in the samples simultaneously in the form of Cr3+ and Cr6+. The catalytic tests were performed in the range of 550–700 °C. The highest selectivity for propylene was observed for the 5%Cr/MCM-41 catalyst and was 76% at a temperature of 650 °C with a propane conversion of 20%. The deposited catalysts Cr/MCM-41 and Cr/SiO2 (Acros) were compared. The propylene selectivity for the MCM-41-supported catalyst was ~1.5 times higher than that for the SiO2-supported catalyst. Full article
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13 pages, 7418 KiB  
Article
Hydroformylation of Alkenes over Phosphorous-Free Rhodium Supported on N-Doped Silica
by Yulia Kardasheva, Maria Terenina, Daniil Sokolov, Natalia Sinikova, Sergey Kardashev and Eduard Karakhanov
Catalysts 2023, 13(5), 818; https://doi.org/10.3390/catal13050818 - 28 Apr 2023
Cited by 2 | Viewed by 1097
Abstract
A new phosphorous-free rhodium supported on a nitrogen-doped silica was successfully used as a catalyst for the hydroformylation of alkenes. The obtained material and the catalyst were characterized by XRD, XPS, FTIR, SEM, TEM, ICP AES, and low-temperature nitrogen adsorption–desorption measurements. The catalytic [...] Read more.
A new phosphorous-free rhodium supported on a nitrogen-doped silica was successfully used as a catalyst for the hydroformylation of alkenes. The obtained material and the catalyst were characterized by XRD, XPS, FTIR, SEM, TEM, ICP AES, and low-temperature nitrogen adsorption–desorption measurements. The catalytic performance was studied by the example of the hydroformylation of octene-1 at temperatures of 80–140 °C and a pressure of 5.0 MPa. The catalyst provided a 99% conversion of 1-octene with a 98% yield of aldehydes and showed a good conversion of styrene and cyclohexene. The catalyst can be repeatedly used in ten consecutive cycles, with its activity remaining constant. Full article
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14 pages, 5486 KiB  
Article
Supported Ionic Liquid Catalysts for the Oxidation of S- and N-Containing Compounds—The Effect of Bronsted Sites and Heteropolyacid Concentration
by Vladislav Gorbunov, Aleksey Buryak, Kirill Oskolok, Andrey G. Popov and Irina Tarkhanova
Catalysts 2023, 13(4), 664; https://doi.org/10.3390/catal13040664 - 28 Mar 2023
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Abstract
In this article, a series of effective catalysts based on betaine and sulfuric or phosphomolybdic acids was obtained. These compositions were characterized by various physicochemical methods and tested in the oxidation of sulfur- and nitrogenous-containing compounds by H2O2. An [...] Read more.
In this article, a series of effective catalysts based on betaine and sulfuric or phosphomolybdic acids was obtained. These compositions were characterized by various physicochemical methods and tested in the oxidation of sulfur- and nitrogenous-containing compounds by H2O2. An increase in the amount of heteropolyacid (HPA) leads to a non-linear change in acidity, and the degree of removal of sulfur-containing compounds correlates with the concentration of Bronsted acid sites on the surface. On the contrary, the degree of pyridine removal is determined primarily by the content of heteropolyacids in the catalyst. Full article
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19 pages, 3252 KiB  
Article
Synthesis and Investigation of Zeolite TiO2/Al-ZSM-12 Structure and Properties
by Dmitry E. Tsaplin, Vera A. Ostroumova, Leonid A. Kulikov, Anna V. Zolotukhina, Alexey A. Sadovnikov, Michail D. Kryuchkov, Sergey V. Egazaryants, Anton L. Maksimov, Kaige Wang, Zhongyang Luo and Evgeny R. Naranov
Catalysts 2023, 13(2), 216; https://doi.org/10.3390/catal13020216 - 17 Jan 2023
Cited by 3 | Viewed by 1872
Abstract
The textural, structural, morphological, and acidic properties of TiO2/Al-ZSM-12 zeolite synthesized viathe hydrothermal method and using methyltriethylammonium chloride as a template were studied in this study. The structure, size, and shape of the crystallites, and the acidity of the synthesized materials [...] Read more.
The textural, structural, morphological, and acidic properties of TiO2/Al-ZSM-12 zeolite synthesized viathe hydrothermal method and using methyltriethylammonium chloride as a template were studied in this study. The structure, size, and shape of the crystallites, and the acidity of the synthesized materials were investigated in detail using the following methods: XRD, low-temperature nitrogen adsorption–desorption, XRF, FTIR, Raman spectroscopy, DRS UV–Vis, DRIFTS, PL, SEM, TEM, solid-state NMR spectroscopy on 27Al, 1H, 29Si, 1H-29Si and 23Na nuclei, NH3-TPD, TG, DSC, DTA, FTIR-Py, FTIR-2,6-dTBP, FTIR-CD3CN, and DRIFTS-acid. The presence of tetrahedral titanium in the TiO2/Al-ZSM-12 zeolite was confirmed by Raman spectroscopy, DRIFT, and 29Si NMR. It was revealed that the crystallites of the TiO2/Al-ZSM-12 zeolite, elongated along the b axis, had a higher acidity compared to the unsubstituted zeolite Al-ZSM-12. The oxidative catalytic activity of the TiO2/Al-ZSM-12 zeolite was studied in the photoinduced decomposition of the crystal violet dye and it was found that the reaction proceeds most efficiently in the presence of H2O2 as an oxidizing agent and TiO2/Al-ZSM-12 as a catalyst (PCA = 0.157%∙min−1). Full article
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Review

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25 pages, 3664 KiB  
Review
Fischer–Tropsch Synthesis Catalysts for Selective Production of Diesel Fraction
by Kristina Mazurova, Albina Miyassarova, Oleg Eliseev, Valentine Stytsenko, Aleksandr Glotov and Anna Stavitskaya
Catalysts 2023, 13(8), 1215; https://doi.org/10.3390/catal13081215 - 16 Aug 2023
Cited by 1 | Viewed by 3011
Abstract
The Fischer–Tropsch process is considered one of the most promising eco-friendly routes for obtaining synthetic motor fuels. Fischer–Tropsch synthesis is a heterogeneous catalytic process in which a synthesis gas (CO/H2) transforms into a mixture of aliphatic hydrocarbons, mainly linear alkanes. Recently, [...] Read more.
The Fischer–Tropsch process is considered one of the most promising eco-friendly routes for obtaining synthetic motor fuels. Fischer–Tropsch synthesis is a heterogeneous catalytic process in which a synthesis gas (CO/H2) transforms into a mixture of aliphatic hydrocarbons, mainly linear alkanes. Recently, an important direction has been to increase the selectivity of the process for the diesel fraction. Diesel fuel synthesized via the Fischer–Tropsch method has a number of advantages over conventional fuel, including the high cetane number, the low content of aromatic, and the practically absent sulfur and nitrogen impurities. One of the possible ways to obtain a high yield of diesel fuel via the Fischer–Tropsch process is the development of selective catalysts. In this review, the latest achievements in the field of production of diesel via Fischer–Tropsch synthesis using catalysts are reviewed for the first time. Catalytic systems based on Al2O3 and mesoporous silicates, such as MCM-41, SBA-15, and micro- and mesoporous zeolites, are observed. Together with catalytic systems, the main factors that influence diesel fuel selectivity such as temperature, pressure, CO:H2 ratio, active metal particle size, and carrier pore size are highlighted. The motivation behind this work is due to the increasing need for alternative processes in diesel fuel production with a low sulfur content and better exploitation characteristics. Full article
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